The subject of this patent application are pesticide formulations which contain carbohydrates which improve the activity and performance of the active material over conventional formulations.

Background

The use of chemical treatments is a common method of improving agricultural yields, quality of product and efficiency. The global market for agrochemicals is estimated to grow to more than 30 billion USD by 2020. The use of pesticides has allowed agricultural output to grow to meet the increasing demand for food. The widespread use of these materials has however raised concerns about the negative environmental and human health impacts of intensive pesticide usage, therefore there has been an ongoing search for materials and methods that address these problems by reducing the amount of active materials that are used in agriculture.

The use of pesticide formulations that contain surfactants, penetrants, stickers and solvents to increase the effectiveness of the active component is well established (I. Travlos, N. Cheimona and D. Bi la I is in Agronomy (2017), Vol. 7 (3); 60-69). These adjuvants aid in the penetration of the active through the dermal layer of the leaf and improve the application characteristics of the product. The formulations may typically include surfactants, antifoaming agents, solvents, stickers, spreaders, penetrants, dyes, odorants, bittering agents, anti-drift agents, humectants and preservatives.

Active herbicide ingredients such as these and others can be prepared from and used in the form of solid and liquid compositions including, as mentioned above, different forms of emulsions, suspensions, suspension concentrates, mixtures, dispersions, microemulsions, etc., and derivatives thereof such as diluted solutions or solutions including other one or more added ingredients, for example herbicides, insecticides, fungicides, nematacides, acaricides, and growth regulators.

In general, an agricultural spray mixture contains water and an active agricultural chemical ingredient, such as a pesticide (including herbicides, insecticides, fungicides and growth regulators). Typically, at least 50 percent of the agricultural spray mixture is composed of water. Optionally, the agricultural spray mixture can contain at least one component selected from the group consisting of organic surfactants, antifoam agents and organic solvents. Agricultural spray mixtures are commercially available as ready- to-use products or can be prepared in a containment vessel from an agricultural chemical concentrate formulation, water, and optionally one or more surfactants and/or antifoaming agents.

For the working of agricultural areas, 100-1000 litres of diluted formulation are generally sprayed per hectare. In exceptional cases, however, these limits can vary greatly upwards or downwards. In so-called low-volume applications very small volumes, for example down to 1.5 I itres/ha are sprayed, whereas in the case of application with so-called lance technology very high volumes up to 15 000 I itres/ha can be achieved. The amount of the active ingredient (i.e. pesticide) in a diluted formulation (spray mixture) will be any amount effective for the intended purpose, but typically will range from about 0.001 to about 5 percent by weight based upon the total weight of the agricultural spray mixture, for example from about 0.03 percent to about 4 percent, preferably from about 0.05 percent to about 2 percent based upon the total weight of the agricultural spray mixture. The bulk or remainder of the agricultural spray mixture is comprised of water.

The atomization process here can take place either from high altitudes, for example by means of the spraying from an aircraft such as an aeroplane, helicopter or remotely piloted drone, or from altitudes close to the earth, for example by spraying by means of a tractor-mounted sprayer. Other equipment, such as spraying lances, or back-spraying are also known for applying spray treatments.

In addition, standard additives such as surfactants, solvents, biocides, antifoam agents, dispersants, antifreeze, pH modifiers, colorants, nutrients and plant growth regulators also may be included in the formulations to achieve desired results.

Contact herbicides such as glyphosate have relatively poor absorption and translocation, primarily due to poor dermal penetration and immobilisation in the leaf, therefore small improvements in absorption and translocation can provide improved efficacy and/or reduced application rates. The subject of this patent application describes formulations using natural biodegradable carbohydrates as efficacy enhancing agents to increase the efficacy of pesticidal products.

Soluble carbohydrates in solid form (e.g. sucrose) has been used as a dispersant in solid formulations (WO 2012/009489A2). The use of carbohydrate derived surfactants such as polyalkylglucosides has been demonstrated as an effective surfactant that aids absorption of glyphosate (WO 2013/189777A1), with alginate being used as a stabilising agent (WO 2011/0328292), pectin being used as agent in formulations (US 6699977B1), pectin being used as a thickener in encapsulated products (RU 2572882C2), pectin for use as a thickener in formulations (CN 102728024A), and protein-polysaccharide used in compositions for providing sustained release formulations (US 5747416A). Cyclodextrin and polymer mixtures have also been used to improve the solubility of actives (US 5472954A). The term "cyclodextrin" stands here for cyclic oligosaccharides formed from glucose molecules connected via a-l,4-glycoside bonds which can be obtained by enzymatic decomposition of starch. They comprise a Greek letter as prefix, depending on the number of glucose molecules from which they are built, a-, [3-, y- and 6-cyclodextrins with 6, 7, 8 or 9 glucose molecules are especially of importance.

Pyrethroid-cyclodextrin complexes have been developed and shown to have greater efficacy than the active material alone (CN 200480031423). Pesticide-cyclodextrin and synergist-cyclodextrin complexes have also been shown to have enhanced efficacy over conventional formulations (WO 2006/111570 A2).

Herbicide resistance has been found to be an emerging problem, with the most researched mechanisms being target site mutation and metabolic resistance, with translocational resistance being the third form. During research into target site resistance and metabolic resistance it was found that many resistant strains also showed reduced export of the glyphosate from the leaves to the roots (D.F. Lorraine Colwill, S. B. Powles, T. R. Hawkes, P. H. Hollinshead, S. A. J. Warner, and C. Preston in Pestic Biochemistry and Physiology (2003) 74: 62-72). Isotope studies to map the movement of glyphosate in plant tissues have showed that immobilisation of glyphosate in resistant Conyza canadendis is the main form of resistance, and that this immobilisation occurs through active ATP-dependent transport of glyphosate into the vacuole by the tonoplast. Investigation has shown that this mechanism is also present in weeds that have been shown to have target-site resistance and metabolic resistance (Ge, Xia et al. in Plant physiology (2014) Vol. 166, 3: 1255-68). The precise mechanism of glyphosate transport is unclear with some researchers proposing a phosphate mechanism (M. Dennis and S. Delrot in Physiologic Plantarum (1993) 87: 569-575), but recent research has provided evidence of glyphosate interacting with sugar transport and metabolism in non-photosynthetic parasitic plants (T. Shilo et al in Frontiers in Plant Science, (2017), Vol. 8, article 255: 1-16).

Sugars have also been shown to have a role in priming plant defences when applied as foliar feeds, with sucrose foliar applications boosting the effectiveness of co-applied fungicides (M. R. B Moghaddam and W Van Den in Journal of Experimental Biology (2012) Vol. 63, 11: 3989-3998) ZA 992373 B (American Cyanamid) discloses solid agricultural compositions comprising a monosaccharide, an oligosaccharide and/or a polysaccharide. The compositions form stable, aqueous dispersions in the presence of polyacrylamide drift control agents.

JP H02129107 A (SDS Biotech) discloses a hard swallowable insecticidal composition containing a methoxyl compound as an active ingredient in order to prevent a poisoning accident caused by accidental swallowing.

WO 2019/008341 Al (Pangaea Agrochemicals Ltd) discloses a method for producing an encapsulated pesticide includes the steps of (a) providing a mixture of a pesticide (such as glyphosate) and at least one polysaccharide in either (i) an organic solvent or(ii) in aqueous solution, (b) combining the mixture of step (a) with water in the case of (i) or an oil in the case of (ii) and stirring to create an emulsion of said mixture, (c) adding to said emulsion a salt (such as calcium chloride) in powder form, which salt is formed of a cation which reacts with said polysaccharide to produce a water-insoluble reactant, and (d) stirring the product of step (c) in order to produce particles of pesticide encapsulated in said water-insoluble reactant.

WO 2020/128511 Al (Pangaea Agrochemicals Ltd) discloses a method for encapsulating a pesticide (for example glyphosate) includes the steps of (a) mixing a first biopolymer which is an alginate with a viscosity from 4 to 100 centipoise (a 1% aqueous solution at 20 centigrade) and a second biopolymer in solution, (b) adding the product of step (a) to a solution of pesticide, and (c) adding a surfactant to the product of step (b). Surfactant levels of at least 3wt% are disclosed.

Surfactants are included in agrochemical formulations to enhance activity against the target pest species. The included surfactants can produce negative effects against beneficial non-target species such as bees, worms and soil biota. [Goodwin, R & McBrydie, H.. (2000). Effect of surfactants on honey bee survival. N Z Plant Prot. New Zealand Plant Protection], Many surfactants are classified as biocides and their application to crops can have negative effects on overall soil health, [van Bruggen, Ariena & MM, He & Shin, Keumchul & V, Mai & Jeong, K.C. & Finckh, Maria & Jr, Morris,. (2018). Environmental and health effects of the herbicide glyphosate. Science of The Total Environment.

616-617. 255-268. 10.1016/j.scitotenv.2017.10.309.]

The present invention seeks to provide improved pesticide formulations with reduced amounts of surfactant. Summary of the Invention

In accordance with a first aspect of the invention, there is provided a pesticide formulation including the following components: i) one or more actives selected from a herbicide, an insecticide, a fungicide, a growth regulator, or any combination thereof; ii) pectin or a derivative thereof; iii) an alginate or a derivative thereof; and iv) less than 3wt% surfactant and preferably no more than 0.5wt% surfactant.

Surprisingly, it has been discovered that an effective pesticide formulation can be provided which has minimal levels of surfactant.

In a preferred embodiment the formulation additionally includes at least one salt of a metal or organic compound. However this could be provided for example by using sufficiently hard water to provide sufficient calcium ions.

The invention disclosed herein describes herbicidal formulations containing carbohydrates (in the form of a combination of pectin and an alginate) which are thought to function to improve the spray characteristics and/or efficacy of the active component by improving the transport of active materials into and through the plant, and/or affecting plant metabolism in a beneficial way. These formulations show advantageous properties compared to conventional formulations; faster speed of action, lower applications rates, enhanced activity against pests that have evolved resistance.

Without wishing to be constrained by theory, it is thought that the use of these carbohydrates improves the adhesion of active materials to the surface of the plant and also aids the mobility of the material as it is actively transported through the plant. A reduced mobility of herbicide (glyphosate) has been observed in metabolic resistant weed strains which have evolved metabolic and/or target site resistance, and this invention seeks to provide a method whereby mobility and activity may be partially or fully restored through the provision of formulations containing soluble carbohydrates combined with herbicidal (or fungicidal or insecticidal) materials. The preferred embodiments are liquid aqueous crop protection agents of water-soluble and or water insoluble plant protection agents, characterized in that they comprise:

A. One or more water-soluble active crop protectant ingredients,

B. Optionally one or more water-insoluble active crop protectant ingredients,

C. A primary carbohydrate of pectin and/or alginate

D. Optionally a secondary carbohydrate,

E. Optionally organic solvents,

F. Non-ionic, cationic, anionic and / or zwitterionic surfactants,

G. Optionally non-ionic surfactants from the group of alkyl polyglycosides,

H. Inorganic salts from the group of ammonium salts, metal salts,

I. Optionally other non-ionic, anionic, cationic and/or zwitterionic surfactants,

J. Optionally other customary formulation assistants, such as anti-foam agents, odorants, colourants, anti-drift agents.

Typically the active material may be a water-soluble herbicide, for example glyphosate, glufosinate, clopyralid, dicamba, triclopyr, imazapyr, metolachlor, etc.

Typically the active material may be a water soluble insecticide,

Typically the active material may be a water soluble fungicide,

Alternatively, at least one active may be provided as an insoluble pesticide in the form of a colloidal suspension, preferably where the size of the particles in suspension is preferably less than 1 micron, or less than 500 nanometres. According to a particular embodiment of the present invention, at least a portion of the active agent is present in the suspension concentrates in the form of dispersed particles, the volume-average diameter of which, determined using dynamic light scattering, is less than 1 pm, for example not more than 900 nm, 800 nm, 700 nm or 500 nm, e.g. from 10 up to <100 nm, 20 to 900 nm, 50 to 800 nm, 70 to 700 nm or 100 to 500 nm.

The mean particle diameters described here are volume-average particle diameters d (0.5) or d (v 0.5), i.e. 50% by volume of the particles have a diameter lying above the mean value given and 50% of the particles have a diameter lying below the mean value given. Such mean particle diameters can be determined using dynamic light scattering, usually carried out on dilute suspensions comprising from 0.01 to 1% by weight of active agent. These methods are known to a person skilled in the art and are described, for example, in H. Wiese (D. Distler, Ed.), Wassrige Polymerdispersionen (Aqueous Polymer Dispersions), Wiley-VCH 1999, Chapter 4.2.1, pp 40ff, and the literature cited therein; H. Auweter and D. Horn, J. Colloid Interf. Sci., 105 (1985), p. 399; D. Lilge and D. Horn, Colloid Polym. Sci. 269 (1991), p. 704; and H. Wiese and D. Horn, J. Chem. Phys. 94 (1991), p. 6429.

Alternatively, the active may be a pesticide in the form of an emulsion of a polar solvent in water, the active being dissolved in the polar solvent.

The term pesticide refers to at least one active substance selected from the group of the fungicides, insecticides, nematicides, herbicides, safeners, and/or growth regulators. Preferred pesticides are fungicides, insecticides, herbicides and growth regulators. Especially preferred pesticides are herbicides and growth regulators. Mixtures of pesticides from two or more of the abovementioned classes may also be used. The skilled worker is familiar with such pesticides, which can be found, for example, in Pesticide Manual, 15th Ed. (2009), The British Crop Protection Council, London. The pesticides may also comprise salts, esters, optical isomers or tautomers. Suitable pesticides are (groups A to N):

A. Respiration inhibitors - complex-lll-inhibitors at the Q0 -site (for example strobilurins): azoxystrobin, coumethoxystrobin, coumoxystrobin, dimoxystrobin, enestroburin, fenaminstrobin, fenoxystrobin/flufenoxystrobin, fluoxastrobin, kresoxim-methyl, metominostrobin, orysastrobin, picoxystrobin, pyraclostrobin, pyrametostrobin, pyraoxystrobin, trifloxystrobin, methyl 2-[2-(2,5-dimethylphenyloxymethyl)phenyl]-3- methoxyacrylate, 2-(2-(3-(2,6-dichlorophenyl)-l-methylallylideneaminooxymethy l)phenyl)-2- methoxyimino-Nmethylacetamide, pyribencarb, triclopyricarb/chlorodincarb, famoxadon, fenamidon; Complex-lll-inhibitors of the Qi-site: cyazofamid, amisulbrom; Complex-ll- inhibitors (for example carboxamides): benodanil, bixafen, boscalid, carboxin, fenfuram, fluopyram, flutolanil, fluxapyroxad, furametpyr, isopyrazam, mepronil, oxycarboxin, penflufen, penthiopyrad, sedaxane, tecloftalam, thifluzamide, N-(4'- trifluoromethylthiobiphenyl-2-yl)-3-difluoromethyl-l-methyl- l H-pyrazole-4-carboxamide and N-(2-(l ,3,3-trimethylbutyl)phenyl)-l ,3-dimethyl-5-fluoro-l H-pyrazole-4-carboxamide; - other respiration inhibitors (for example complex I, uncouplers): diflumetorim; nitrophenyl - derivatives: binapacryl, dinobuton, dinocap, fluazinam; ferimzone; organometal compounds: fentin salts such as fentin acetate, fentin chloride or fentine hydroxide; ametoctradin; and silthiofam; B. Sterol biosynthesis inhibitors (SBI fungicides) C14-Demethylase inhibitors (DMI fungicides): - triazoles: azaconazole, bitertanol, bromuconazole, cyproconazole, difenoconazole, diniconazole, diniconazole-M, epoxiconazole, fenbuconazole, fluquinconazole, flusilazole, flutriafol, hexaconazole, imibenconazole, ipconazole, metconazole, myclobutanil, oxpoconazole, paclobutrazole, penconazole, propiconazole, prothioconazole, simeconazole, tebuconazole, tetraconazole, triadimefon, triadimenol, triticonazole, uniconazole; imidazoles: imazalil, pefurazoate, prochloraz, triflumizole; pyrimidines, pyridines and piperazines: fenarimol, Nuarimol, pyrifenox, triforine; - deltal4-reductase inhibitors: aldimorph, dodemorph, dodemorph acetate, fenpropimorph, tridemorph, fenpropidin, piperalin, spiroxamine; 3-ketoreductase inhibitors: fenhexamid;

C. Nucleic acid synthesis inhibitors - phenylamides or acylamino acid fungicides: benalaxyl, benalaxyl-m, kiralaxyl, metalaxyl, metalaxyl-m (mefenoxam), ofurace, oxadixyl; - others: hymexazole, octhilinone, oxolinic acid, bupirimate;

D. Cell division and cytoskeleton inhibitiors - tubulin inhibitors such as benzimidazoles, thiophanates: benomyl, carbendazim, fuberidazole, thiabendazole, thiophanate-methyl; triazolopyrimidines: 5-chloro-7-(4-methylpiperidin-l -yl)-6-(2,4,6-trifluorophenyl)-[l ,2,4]triazolo[l ,5-a]pyrimidine; - further cell division inhibitors: diethofencarb, ethaboxam, pencycuron, fluopicolid, zoxamid, metrafenon, pyriofenon;

E. Amino acid synthesis and protein synthesis inhibitors - methionine synthesis inhibitors (anilinopyrimidine): cyprodinil, mepanipyrim, pyrimethanil; - protein synthesis inhibitors: blasticidin-S, kasugamycin, kasugamycin hydrochloride hydrate, mildiomycin, streptomycin, oxytetracyclin, polyoxin, validamycin A;

F. Signal transduction inhibitors - MAP/histidine kinase inhibitors: fluoroimide, iprodione, procymidone, vinclozolin, fenpiclonil, fludioxonil; - G-protein inhibitors: quinoxyfen;

G. Lipid and membrane synthesis inhibitors - Phospholipid biosynthesis inhibitors: edifenphos, iprobenfos, pyrazophos, isoprothiolane; - Lipid peroxidation: dicloran, quintozene, tecnazene, tolclofos-methyl, biphenyl, chloroneb, etridiazole; - Phospholipid biosynthesis and cell wall attachment: dimethomorph, flumorph, mandipropamid, pyrimorph, benthiavalicarb, iprovalicarb, valifenalate and 4-fluorophenyl N-(l -(1 -(4- cyanophenyl)ethanesulfonyl)but-2-yl)carbamate; - Compounds which affect cell membrane permeability and fatty acids: propamocarb, propamocarbhydrochloride H. "Multi-Site" inhibitors - inorganic active substances: Bordeaux mixture, copper acetate, copper hydroxide, copper oxychloride, basic copper sulfate, sulfur; Thio- and dithiocarbamates: ferbam, mancozeb, maneb, metam, metiram, propineb, thiram, zineb, ziram; - organochlorine compounds (for example phthalimides, sulfamides, chloronitriles): anilazine, chlorothalonil, captafol, captan, folpet, dichlofluanid, dichlorophen, flusulfamide, hexachlorobenzene, pentachlorophenol and its salts, phthalid, tolylfluanid, N-(4-chloro-2- nitrophenyl)-N-ethyl-4-methylbenzenesulfonamide; - guanidines and others: guanidine, dodine, dodine free base, guazatin, guazatin acetate, iminoctadin, iminoctadin triacetate, iminoctadin tris(al besilate), dithianon;

I. Cell wall biosynthesis inhibitors - glucan synthesis inhibitors: validamycin, polyoxin B; melanin synthesis inhibitors: pyroquilon, tricyclazole, carpropamid, dicyclomet, fenoxanil;

J. Resistence inductors - acibenzolar-S-methyl, probenazol, isotianil, tiadinil, prohexadione- calcium; phosphonates: fosetyl, fosetyl-aluminum, phosphorous acid and its salts;

K. Unknown mode of action 5 - bronopol, quinomethionate, cyflufenamid, cymoxanil, dazomet, debacarb, diclomezin, difenzoquat, difenzoquat-methyl sulfate, diphenylamine, fenpyrazamine, flumetover, flusulfamid, flutianil, methasulfocarb, nitrapyrin, nitrothal- isopropyl, oxine-copper, proquinazid, tebufloquin, tecloftalam, triazoxide, 2-butoxy-6-iodo- 3-propylchromene-4-one, N-(cyclopropylmethoxyimino-(6-difluoromethoxy-2,3- difluorophenyl)methyl)-2-phenyl0 acetamide, N'-(4-(4-chloro-3-trifluoromethylphenoxy)-2,5- dimethylphenyl)-N-ethyl-Nmethylformamidine, N'-(4-(4-fluoro-3-trifluoromethylphenoxy)- 2,5-dimethylphenyl)-N-ethyl-Nmethylformamidine, N'-(2-methyl-5-trifluoromethyl-4-(3- trimethylsilanylpropoxy)phenyl)-Nethyl-N-methylformamidine, N'-(5-difluoromethyl-2- methyl-4-(3-trimethylsilanylpropoxy)phenyl)-N-ethyl-N-methyl formamidine, 5 N-methyl-(l ,2,3,4-tetrahydronaphthalen-l -yl )-2-{l -[2-(5-methyl-3-trifluoromethylpyrazol-l - yl)acetyl]piperidin-4-yl}thiazole-4-carboxylate, N-methyl-(R)-l ,2,3,4-tetrahydronaphthalenl- yl 2-{l -[2-(5-methyl-3-trifluoromethylpyrazol-l -yl)acetyl]piperidin-4-yl}thiazole-4- carboxylate, l-[4-[4-[5-(2,6-difluorophenyl)-4,5-dihydro-3-isoxazolyl]-2- thiazolyl]-l - piperidinyl]-2-[5-methyl-3-(trifluoromethyl)-l H-pyrazol-l-yl]ethanone, 6-tert-butyl-8-fluoro- 2,3- 0 dimethylquinolin-4-yl methoxyacetate, A/-methyl-2-{l-[(5-methyl-3-trifluoromethyl-l H-pyrazoll-yl)acetyl]piperidin-4-yl}-A/-[(l R)-l ,2,3,4-tetrahydronaphthalen-l -yl]-4- thiazolecarboxamide, 3-[5-(4-methylphenyl)-2,3-dimethylisoxazolidin-3-yl]-pyridin e, 3-[5-(4- chlorophenyl)-2,3- dimethylisoxazolidin-3-yl]-pyridine (pyrisoxazol), N-(6-methoxypyridin-3- yl) cyclopropanecarboxamide, 5-chloro-l -(4,6-dimethoxypyrimidin-2-yl)-2-methyl-l H-ben5 zoimidazole, 2-(4-chlorophenyl)-N-[4-(3,4-dimethoxyphenyl)isoxazol-5-yl]- 2-prop-2- ynyloxyacetamide;

L. Growth regulators abscisic acid, amidochlor, ancymidole, 6-benzylaminopurine, brassinolide, butralin, chlormequat (chlormequat chloride), choline chloride, cyclanilid, daminozide, dikegulac, dimethipin, 2,6- dimethylpuridine, ethephon, flumetralin, flurprimidol, fluthiacet, forchlorfenuron, gibberellic acid, inabenfid, indole-3-acetic acid, maleic hydrazide, mefluidid, mepiquat (mepiquat chloride), metconazole, naphthaleneacetic acid, N-6-benzyladenine, paclobutrazole, prohexadione (prohexadione-calcium), prohydrojasmone, thidiazuron, triapenthenol, tributylphosphorotrithioate, 2,3,5-triiodobenzoic acid, trinexapac-ethyl and uniconazole;

M. Herbicides - acetamide: acetochlor, alachlor, butachlor, dimethachlor, dimethenamid, flufenacet, mefenacet, metolachlor, metazachlor, napropamid, naproanilid, pethoxamid, pretilachlor, propachlor, thenylchlor; - amino acid analogs: bilanafos, glyphosate, glufosinate, sulfosate; - aryloxyphenoxypropionat.es: clodinafop, cyhalofop-butyl, fenoxaprop, fluazifop, haloxyfop, metamifop, propaquizafop, quizalofop, quizalofop-P- tefuryl; - bipyridyls: diquat, paraquat; - carbamates and thiocarbamates: asulam, butylate, carbetamide, desmedipham, dimepiperat, eptam (EPTC), esprocarb, molinate, orbencarb, phenmedipham, prosulfocarb, pyributicarb, thiobencarb, triallate; - cyclohexanediones: butroxydim, clethodim, cycloxydim, profoxydim, sethoxydim, tepraloxydim, tralkoxydim; - dinitroanilines: benfluralin, ethalfluralin, oryzalin, pendimethalin, prodiamine, trifluralin; - diphenyl ethers: acifluorfen, aclonifen, bifenox, diclofop, ethoxyfen, fomesafen, lactofen, oyfluorfen; - hydroxybenzonitriles: bromoxynil, dichlobenil, ioxynil; - imidazolinones: imazamethabenz, imazamox, imazapic, imazapyr, imazaquin, imazethapyr; - phenoxyacetic acids: clomeprop, 2,4-dichlorophenoxyacetic acid (2,4-D), 2,4-DB, dichlorprop, MCPA, MCPA- thioethyl, MCPB, mecoprop; - pyrazines: chloridazon, flufenpyr-ethyl, fluthiacet, norflurazon, pyridate; - pyridines: aminopyralid, clopyralid, diflufenican, dithiopyr, fluridone, fluroxypyr, picloram, picolinafen, thiazopyr; - sulfonylureas: amidosulfuron, azimsulfuron, bensulfuron, chlorimuron-ethyl, chlorsulfuron, cinosulfuron, cyclosulfamuron, ethoxysulfuron, flazasulfuron, flucetosulfuron, flupyrsulfuron, foramsulfuron, halosulfuron, imazosulfuron, iodosulfuron, mesosulfuron, metsulfuron-methyl, nicosulfuron, oxasulfuron, primisulfuron, prosulfuron, pyrazosulfuron, rimsulfuron, sulfometuron, sulfosulfuron, thifensulfuron, triasulfuron, tribenuron, trifloxysulfuron, triflusulfuron, tritosulfuron, l-((2-chloro-6- propylimidazo[l ,2-b]pyridazin-3-yl)sulfonyl)-3-(4,6- dimethoxypyrimidin-2-yl)urea; - triazines: ametryne, atrazine, cyanazine, dimethametryne, ethiozine, hexazinone, metamitron, metribuzine, prometryne, simazine, terbuthylazine, terbutryne, triaziflam; - ureas: chlortoluron, daimuron, diuron, fluometuron, isoproturon, linuron, methabenzthiazuron, tebuthiuron; - other acetolactate synthase inhibitors: bispyribac- sodium, cloransulam-methyl, diclosulam, florasulam, flucarbazone, flumetsulam, metosulam, orthosulfamuron, penoxsulam, propoxycarbazone, pyribambenz-propyl, pyribenzoxim, pyriftalide, pyriminobac-methyl, pyrimisulfan, pyrithiobac, pyroxasulfon, pyroxsulam; - others: amicarbazone, aminotriazole, anilofos, beflubutamid, benazolin, bencarbazone, benfluresate, benzofenap, bentazone, benzobicyclon, bromacil, bromobutide, butafenacil, butamifos, cafenstrole, carfentrazone, cinidon-ethlyl, chlorthal, cinmethylin, clomazone, cumyluron, cyprosulfamid, dicamba, difenzoquat, diflufenzopyr, Drechslera monoceras, endothal, ethofumesate, etobenzanid, fentrazamide, flumiclorac- pentyl, flumioxazin, flupoxam, fluorochloridon, flurtamon, indanofan, isoxaben, isoxaflutol, lenacil, propanil, propyzamide, quinclorac, quinmerac, mesotrione, methylarsenic acid, naptalam, oxadiargyl, oxadiazone, oxaziclomefon, pentoxazone, pinoxaden, pyraclonil, pyraflufen-ethyl, pyrasulfotol, pyrazoxyfen, pyrazolynate, quinoclamin, saflufenacil, sulcotrione, sulfentrazone, terbacil, tefuryltrione, tembotrione, thiencarbazone, topramezone, 4-hydroxy-3-[2-(2- methoxyethoxymethyl)-6-trifluoromethylpyridin-3- carbonyl]bicyclo[3.2.1]oct-3-en-2-one, ethyl (3-[2-chloro-4-fluoro-5-(3-methyl-2,6-dioxo-4- trifluoromethyl-3,6-dihydro-2H-pyrimidin- l-yl)phenoxy]pyridin-2-yloxy)acetate, methyl 6- amino-5-chloro-2-cyclopropylpyrimidine-4- carboxylate, 6-chloro-3-(2-cyclopropyl-6- methylphenoxy)pyridazin-4-ol, 4-amino-3-chloro-6-(4- chlorophenyl)-5-fluoropyridin-2- carboxylic acid, methyl 4-amino-3-chloro-6-(4-chloro-2-fluoro3-methoxyphenyl)pyridin -2- carboxylate and methyl 4-amino-3-chloro-6-(4-chloro-3- dimethylamino-2- fluorophenyl)pyridin-2-carboxylate;

N. Insecticides - organo(thio)phosphates: acephate, azamethiphos, azinphos-methyl, chlorpyrifos, chlorpyrifos-methyl, chlorfenvinphos, diazinon, dichlorvos, dicrotophos, dimethoat, disulfoton, ethion, fenitrothion, fenthion, isoxathion, malathion, methamidophos, methidathion, methyl-parathion, mevinphos, monocrotophos, oxydemeton-methyl, paraoxon, parathion, phenthoate, phosalone, phosmet, phosphamidon, phorate, phoxim, pirimiphosmethyl, profenofos, prothiofos, sulprophos, tetrachlorvinphos, terbufos, triazophos, trichlorfon; - carbamates: alanycarb, aldicarb, bendiocarb, benfuracarb, carbaryl, carbofuran, carbosulfan, fenoxycarb, furathiocarb, methiocarb, methomyl, oxamyl, pirimicarb, propoxur, thiodicarb, triazamate; - pyrethroids: allethrin, bifenthrin, cyfluthrin, cyhalothrin, cyphenothrin, cypermethrin, alphacypermethrin, beta-cypermethrin, zeta-cypermethrin, deltamethrin, esfenvalerate, etofenprox, fenpropathrin, fenvalerate, imiprothrin, lambda-cyhalothrin, permethrin, prallethrin, pyrethrin I and II, resmethrin, silafluofen, tau-fluvalinate, tefluthrin, tetramethrin, tralomethrin, transfluthrin, profluthrin, dimefluthrin, - insect growth inhibitors: a) chitin synthesis inhibitors: benzoylureas: chlorfluazuron, cyramazin, diflubenzuron, flucycloxuron, flufenoxuron, hexaflumuron, lufenuron, novaluron, teflubenzuron, triflumuron; buprofezin, diofenolan, hexythiazox, etoxazole, clofentazin; b) ecdysone antagonists: halofenozide, methoxyfenozide, tebufenozide, azadirachtin; c) juvenoids: pyriproxyfen, methoprene, fenoxycarb; d) lipid biosynthesis inhibitors: spirodiclofen, spiromesifen, spirotetramate; - nicotine receptor agonists/antagonists: clothianidin, dinotefuran, imidacloprid, thiamethoxam, nitenpyram, acetamiprid, thiacloprid, l-(2-chlorothiazol-5-ylmethyl)-2- nitrimino-3,5-dimethyl- [ 1 ,3,5]triazinane; - GABA antagonists: endosulfan, ethiprole, fipronil, vaniliprole, pyrafluprole, pyriprole, N-5-amino-l-(2,6-dichloro-4-methylphenyl)-4- sulfinamoyl-1 H-pyrazole-3-thiocarboxamide; - macrocyclic lactones: abamectin, emamectin, milbemectin, lepimectin, spinosad, spinetoram; - mitochondrial electron transport chain inhibitor (METI) I acaricides: fenazaquin, pyridaben, tebufenpyrad, tolfenpyrad, flufenerim; - METI II and III substances: acequinocyl, fluacyprim, hydramethylnone; - decouplers: chlorfenapyr; - inhibitors of oxidative phosphorylation: cyhexatin, diafenthiuron, fenbutatin oxide, propargite; - insect ecdysis inhibitors: cryomazin; - 'mixed function oxidase' inhibitors: piperonyl butoxide; - sodium channel blockers: indoxacarb, metaflumizon; - others: benclothiaz, bifenazate, cartap, flonicamid, pyridalyl, pymetrozin, sulfur, thiocyclam, flubendiamid, chlorantraniliprole, cyazypyr (HGW86); cyenopyrafen, flupyrazofos, cyflumetofen, amidoflumet, imicyafos, bistrifluron and pyrifluquinazone.

The carbohydrate employed in the present formulation includes pectin and an alginate in combination. It may additionally include a further (third) carbohydrate. Typically the additional carbohydrate preferably may be sucrose, dextrose, cyclodextrose, glucose, xylose, maltose, lactose, starch, xylan, hemicellulose, maltitol, sorbitol, or mixtures of two or more of these carbohydrates. Typically, these sugars will be provided in the form of an aqueous solution.

Typically the carbohydrate may comprise 1-25% by weight of the formulation.

Typically the formulation may contain one or more active materials, carbohydrates, organic or inorganic salts, organic surfactants, anti-foam agents, anti-drift agents, stabilising agents, preservatives, penetrants, oils, dyes, fragrance, bittering agents etc.

Although the preferred formulations include 0wt% surfactant, formulations in accordance with the invention may include up to 0.5wt% surfactant as defined below:

Typically the surfactants may be anionic, cationic or non-ionic surfactants, such as polyalkyl glucosides, polyoxypropylene-polyoxyethylene block copolymers, alkyl-trimethyl and dialkyldimethyl quaternary ammonium salts, cocoamine ethoxylates, organosilicone surfactants, fatty acid esters, alkylphenolethoxylates, Polyetheralkanolamine comb polymers, stearyl amine ethoxylates, or any other suitable surfactant. The surfactants preferably may be sugar-based surfactants containing sorbitans, ethoxylated sorbitans, sucrose esters, glucose esters, or alkyl polyalkylglucosides.

The surfactants preferably may be cocoamine ethoxylates.

The formulations of the invention contain as surfactant anionic, cationic or zwitterionic and/or nonionic surface-active compounds (surfactants) which should contribute to improved stability, availability for the plants, or activity of the formulated crop protection active ingredients.

Examples of anionic surfactants are (where EO = ethylene oxide units, PO = propylene oxide units and BO = butylene oxide units):

A. Anionic derivatives of fatty alcohols with 10-24 carbon atoms with 0-60 EO and / or 0-20 PO and / or 0-15 BO in any desired sequence in the form of ether carboxylates, sulfonates, sulfates and phosphates and their inorganic salts (for example, alkali and alkaline earth metal) and organic salts (for example based on amine or alkanolamine) such as Genapol ’ LRO, Sandopan ’ brands, Hostaphat / Hordaphos ’ brands from Clariant;

B. Anionic derivatives of fatty alcohols with 10-24 carbon atoms with 0-60 EO and / or 0-20 PO and / or 0-15 BO in any desired sequence in the form of ether carboxylates, sulfonates, sulfates and phosphates and their inorganic salts (for example, alkali and alkaline earth metal) and organic salts (for example based on amine or alkanolamine) such as Genapol ’ LRO, Sandopan ’ brands, Hostaphat / Hordaphos ’ brands from Clariant;

C. Anionic derivatives of copolymers consisting of EO, PO and / or BO units having a molecular weight of 400 to 10 ⁸ in the form of ether carboxylates, sulfonates, sulfates and phosphates and their inorganic salts (for example alkali and alkaline earth metal) and organic salts (for example based on amine or alkanolamine);

D. Anionic derivatives of alkylene oxide adducts of C i -C ₉ alcohols in the form of ether carboxylates, sulfonates, sulfates and phosphates and their inorganic salts (for example alkali and alkaline earth metal) and organic salts (for example based on amine or alkanolamine);

E. Anionic derivatives of fatty acid alkoxylates in the form of ether carboxylates, sulfonates, sulfates and phosphates and their inorganic salts (for example alkali and alkaline earth metal) and organic salts (for example based on amine or alkanolamine); Preferred anionic surfactants are alkyl polyglycol ether sulfates, in particular Fettalkoholdiethylenglykolethersulfat (z. B. Genapol LRO *' Clariant), or Alkylpolyglykolethercarboxylate (z. B. 2- (Isotridecyloxy-polyethyleneoxy) ethyl- carboxymethyl-ether, Marlowet 4538 ’ Huis)

Examples of cationic or zwitterionic surfactants are (where EO = ethylene oxide units, PO = propylene oxide units and BO = butylene oxide units):

A. Alkylene oxide adducts of fatty amines, quaternary ammonium compounds with 8 to 22 carbon atoms (C _g -C 22) such as Genamin ’ C, L, O, T brands by Clariant;

B. Surface-active, zwitterionic compounds such as taurides, betaines and sulfobetaines in the

® ® ® form of Tegotain brands by Goldschmidt, Hostapon T and Arkopon T brands by Clariant.

Examples of non-ionic surfactants are:

A. Fatty alcohols having 10-24 carbon atoms with 0-60 EO and / or 0-20 PO and / or 0-15 BO in any desired sequence. Examples of such compounds are Genapol ’ C, L, O, T, UD, UDD, X © © > > © brands by Clariant, Plurafac - and Lutensol A, AT, ON, TO brands by BASF, Marlipal 24 and 013 brands by Condea, Dehypon ’ brands by Henkel, Ethylan ’ brands from Akzo-Nobel such as Ethylan CD 120;

B. Fatty acid and triglyceride as the Serdox NOG ’ brands by Condea or the Emulsogen ’ brands from Clariant;

C. Fatty acid such as the Comperlan ’ brands from Henkel or the Amam ’ brands from Rhodia;

D. Alkylene oxide adducts of alkyne diols such as the Surfynol ’ grades from Air Products; Sugar derivatives such as amino and amido sugars from Clariant;

E. Glucitols from Clariant;

F. Surface-active compounds based on silicone or silane, such as the Tegopren ’ brands from Goldschmidt and the SE brands from Wacker, as well as Bevaloid Rhodorsil - and Silcolapse ’ brands from Rhodia (Dow Corning, Reliance, GE, Bayer)

G. Surface-active sulfonamides, eg from Bayer;

H. Surface-active polyacrylic and polymethacrylic derivatives such as the Sokalan * brands from BASF;

I. Surface-active polyamides such as modified gelatin or derivatized polyaspartic acid from Bayer and their derivatives,

J. Surfactant polyvinyl compounds such as modified PVP as the Luviskol * brands from BASF and the Agrimer ’ brands from ISP or the derivatized polyvinyl acetates such as the Mowilith ’ brands from Clariant or the butyrates such as the Lutonal ’ brands from BASF , the Vinnapas ’ - and the Pioloform ’ brands from Wacker or the modified polyvinyl alcohols such as the Mowiol * brands from Clariant,

K. Surface-active polymers based on maleic anhydride and / or reaction products of maleic anhydride, and maleic anhydride and / or reaction products of maleic anhydride-containing copolymers such as the Agrimer ’ VEMA brands by ISP, L. Surface-active derivatives of montan, polyethylene and polypropylene waxes such as the Hoechst waxes ’ or Licowet * brands from Clariant,

M. Sorbitan esters in the form of clamping ’ - ’ or Tween brands from Uniquema or cyclodextrin esters or ethers from Wacker,

N. Surface-active cellulose, algin, pectin and guar derivatives such as the Tylose ’ brands from Clariant, the Manutex ’ grades from Kelco and guar derivatives from Cesalpina,

O. Alkylene oxide adducts based polyol such as polyglycol ’ brands from Clariant,

P. Surface-active polyglycerides and their derivatives from Clariant.

The formulations of the invention contain may non-ionic surfactants from the group of alkyl polyglycosides.

A. Alkylpolysaccharides, and mixtures thereof, such as from the Atplus * series from Uniqema, preferably Atplus 435

B. Alkylpolyglycosides ’ in the form of the APG brands from Henkel, for example APG Plantaren * 225 (fatty alcohol C ₈ -C ₁₀ glucoside),

C. Sorbitan esters in the form of clamping * - ’ or Tween brands from Uniquema,

D. Cyclodextrin esters or ethers from Wacker,

E. Surface-active cellulose and algin, pectin and guar derivatives such as the Tylose ’ brands from Clariant, the Manutex ’ grades from Kelco and guar derivatives from Cesalpina,

F. Alkyl polyglycoside alkyl polysaccharide mixtures based on C ₈ -C _xo fatty alcohol such as ’ Glucopon 225 DK * and Glucopon 215 CSUP (Cognis).

The anti-drift agents may preferably be polymers, such as polyethylene glycol,

Typically the formulation will include antifoaming agents. Examples of antifoaming agents are silicone emulsions (such as, e.g., Silikon® SRE, from Wacker or Rhodorsil® from Rhodia), long-chain alcohols, fatty acids, salts of fatty acids, e.g. magnesium stearate, fluoro-organic compounds and the mixtures thereof. Typically the formulation can also comprise dyes (colorants). Examples of colorants are both pigments which are sparingly soluble in water and colorants which are soluble in water. Mention may be made, as examples, of the colorants known under the descriptions Rhodamine B, C.l.

Pigment Red 112 and C.l. Solvent Red 1, and also Pigment Blue 15:4, Pigment Blue 15:3, Pigment Blue 15:2, Pigment Blue 15:1, Pigment Blue 80, Pigment Yellow 1, Pigment Yellow 13, Pigment Red 112, Pigment Red 48:2, Pigment Red 48:1, Pigment Red 57:1, Pigment Red 53:1, Pigment Orange 43, Pigment Orange 34, Pigment Orange 5, Pigment Green 36, Pigment Green 7, Pigment White 6, Pigment Brown 25, Basic Violet 10, Basic Violet 49, Acid Red 51, Acid Red 52, Acid Red 14, Acid Blue 9, Acid Yellow 23, Basic Red 10 and Basic Red 108.

Typically the formulation will be used as an aqueous solution for application by sprayer onto the target plants.

Typically the formulation may preferably be provided as a concentrate for dilution with water prior to application. The ready-to-dilute formulation of the subject invention may be utilized in tank mixes for many pesticide formulations, generally in amounts of from about 0.5 to about 8 L/ha, preferably from about 1 to about 10 L/ha.

Typically the formulation may be provided as a two part concentrate for use as a tank-mix where the adjuvant components and actives are in separate solutions and are mixed with the actives and diluted with tap water immediately prior to use.

In an alternative embodiment of the invention, there is provided a pesticide formulation that comprises: i) one or more active components which may be herbicides, insecticides, fungicides or growth regulators; ii) pectin or a derivative thereof; iii) an alginate or a derivative thereof; iv) at least one surfactant; v) at least one salt of a metal or organic compound. A number of preferred embodiments of the present invention will now be described, with reference to and as illustrated in the accompanying drawings, in which:

Figure 1 is a bar graph showing the results of a trial of a pesticide in accordance with the invention and comparative pesticides; and Figure 2 is a bar graph showing the results of a trial of comparative pesticides.

EXPERIMENTAL

Formulation 1 - Pangaea Enigma Eco Zero 360g/l glyphosate formulation

All volumes are given per litre of final product.

Pectin was added to 300ml water heated to 80°C. Then the sodium alginate was added with stirring and the mixture heated to 95°C and stirring continued until the solids has dissolved.

Then glycerol was added to the stirred mixture. Glyphosate as an aqueous solution of the isopropylamine (IPA) salt was added to the mixture while stirring continued. Finally, citrus scent was added and the mixture allowed to cool. Total 1023g - 1.00L

Formulation 1 is surfactant-free.

Comparative Formulation 2 - Pangaea Enigma Eco 360g/l glyphosate formulation

Formulation 2 was prepared as for Formulation 1 except that a surfactant (LKD 1559) was added to result in a final amount of surfactant of 4wt%.

Comparative Formulation 3 - Gallup ⁸ XL 360g/l glyphosate and ammonium sulphate

This is a commercially available weedkiller (Barclays Crop Protection) and is thought to have at least 15% surfactant (and possibly more) although the exact amount is a commercial secret.

TRIALS

Trials were carried out using Formulations 1-3.

-Products were added to the tank in accordance with the manufacturer's instructions.

-The tank was half filled with water and buffering applied before the active ingredient is added. The remaining water was then added and the tank agitated.

-The tank was agitated prior to and during spraying.

-A medium nozzle was used.

Rates: 360, 720, 1080 and 1440 grams per hectare applied in 200L of water per hectare.

Trial 1 - Rockland St Mary: 6 and 16 days after spraying (DAS)

The aim of this trial is to assess the efficacy of the Pangaea Enigma Eco 360 glyphosate and Enigma Eco Zero 360 formulations (in a 360g/l SL formulation) against a reference application of a conventional glyphosate formulation.

Application of the glyphosate formulations is made to the weeds in a (field margin, fallow field, longstanding pasture), at 360, 720, 1,080 and 1440 g ai/ha. The weed control achieved with the Pangaea formulations are compared to the reference product Gallup XL (Barclay Crop Protection) applied at rates of 720g, 1080 and of 1440g ai/ha. The trial is located at Rockland St. Mary Norfolk/Suffolk, UK.

Grass and broadleaf species, annual and perennials, in a permanent pasture grass in Norfolk. The application data are shown in Table 1 below:

Table 1 Recording

• Record phytotoxicity symptoms occurring on the treated weeds throughout the trial. These symptoms may be seen as yellowing-necrosis. Use a visual scale 1-10 according to the severity of the symptoms • Record any visible regrowth (greening), if seen in the trial

• Provide photographic evidence

• Assessment timings at 6 and 16 days after spraying (DAS)

It is essential that the time, date and prevailing weather conditions of each trial is recorded together with the temperature at the time of first spray, the temperature at the time of second spray and the peak temperature in the period between spraying. It is also essential that the quantity of water buffering required is also recorded, and is the minimum volume that can be feasibly used.

The results are shown in Figure 1. It can be seen from the yellowing score that the effectiveness of the surfactant-free Formulation 1 was as good (and in many cases better than) Formulations 2 and 3 which includes 4wt% and 15wt%+ surfactant. Trial 2 - Wickhambrook

This trial was carried out according to the same method as Trial 1, but with comparative formulations 2 and 3 only.

The application data are shown in Table 2 below.

Table 2

The results are shown in Figure 2. It can be seen that the effectiveness of comparative formulations 2 & 3 was comparable despite the different amounts of surfactant present.

All optional and preferred features and modifications of the described embodiments and dependent claims are usable in all aspects of the invention taught herein. Furthermore, the individual features of the dependent claims, as well as all optional and preferred features and modifications of the described embodiments are combinable and interchangeable with one another.

The disclosures in UK patent application number 2018938.7 from which this application claims priority, and in the abstract accompanying this application are incorporated herein by reference.